Solids recovery from a polymer solution



March 29, 1960 w. l.. sTALDER Y2,930,787

soLIns RECOVERY FROM A POLYMER soLUTIoN Filed Dec. 28, 1956 somos POLYMER SOLUTION I HOJDVEB )v N 1NvENToR. v 5 mLsrALoER 5 5 BY ATTORNEYS a polymer solution.

mixture is heated whereby polymer associated wi sgsi" sonms RECOVERY Fao-Mn PoLYMEn soLUrIoN Wiiiiafm L. steriler, nmiesvinegoldaj., asstgnqrrorniinis Petroleum Companys corporation of Delaware Application neeember 2s, i956-, seriaiNo: 651,165 6 claims. (ci. 26o-$21.5)

This invention relates to the recovery of solids' from l'n one aspect it relates t the recovery of, sub-divided catalyst solids from a solution of solid olefin polymer by agglomerating sa'id solids with Vprecipitated polymer.

In certain methods of preparing solid polymers, such as polymers of ethylene, the product is obtained as "a solution of polymer in a solvent or dilefnt material and contains finely divided catalyst solids. Generally, it is desirable that the nal polymer product be free of c'a'talyst solids and it may be further desirable to recover the catalyst for re-use in the polymerization reaction. lt has been found that recovery of the cz'ttalyst is facilitated yby agglomerating the catalyst as described in the copending application of Hanson and Croire'y, vSerial No. 572,310,111ed March 19,1956. p e l It isthe object of this invention to provide a itilproved process for the recovery of solids from a' polymer solution. n I

Another object of this invention is to pr''vid an improved process for the recovery Vot catalyst solids from a polymer solution by agglomeration. v

Still another object of this invention is to provide an improved process for the recovery of's'ub-divided catalysts solids by agglomration from a solution f solid ethylene polymer.

These and other objects of the invention will become more readily apparent from the following detailed description and discussion. The foregoing objects are achieved, broadly, by re,-

du'cing the temperature of a solids-containing polymer K solution whereby polymer precipitates from solution the solids agglomerate; thereafter increasing the ternperature o' the 'solution whereby la portion V of the Vpreycip'ated polymer contained in the vagglomerated solids is redi'ssolved and separating the aggloinerate'd solids from the polymersolution. Y f 'd In one `aspect of the invention a snill fa'inoiint of'solv'ent is'added tothe yseparated Ia"glc'ainei'ated solids, the 4' the agglomerated solids is dissolved and thevsolids 'sparated from the dissolved polymer. The dissolved Jtily-I rner can be combined with the polymer solutiontrorn the tirst solids separation step or recovered as a separate 'product'. l l

This invention is applicable in' general to the treatment of olen polymers such as, for example, polymers or copolymers of monoolelins like ethylene, propylene, butylene, etc.;` also,` copolymers Vof monoolelins and dioleins such as butadiene, isoprene, etc. These polymers are prepared usually by contacting the olefin to be polyinerized with a catalyst in the presence ofja solvent or d iluent material at an elevated temperature and pressure.

' AA iiu'rnber of catalyticmaterials can be used fortheipurpese of polymerizing olefins, the most desirable bemg Lchromiurri oxide, preferably containing hexavalent chromium, with silica, alumina, zirconia, thoria, silica-alumina, etc. These catalysts can be prepared, for examj so i 15 minutes anna-beur 12 hours; l

` f per molecule,

t watchers martienne-srt and int-H'evl'iq'uid vICC f Patented Mark.2 29, v196? vconditions (eg. in" anhydrous air) tor several hours.

For a detailed discussion -oi? the catalysts', their composition and their methods of preparation, reference can be had tothe copending application of Hogan and' Banks, Serial No: 573,877, now U.S. 2,825,721,` tiled March 26 1956', wherein the catalysts are discussed in detail.

- These andy other s'olid catalysts or catalysts containing l'a -solid component can' be treated in theV method o'f'this invention.

The temperature required for polymerizing Yoleli'ns variesl over Ta wide `raiige. However; usuallyit isp'referrd to ca'rry .out the reacti'n at av-temperatu`re between about F. and about 450 F.- IThe?partic'z'ular temperature to be employed in each individual 'casadepends on tliecat'alyst used, 'the olen to bel'polyineriz'd and the operating conditions employed, such as'l pressure, :space lvelocity, diluent to ol'en ratio, etc.V

The "polymerization pressure usually isI 'maintained at vav suliicient levell 'to assure a liquid phase'y reaction,` that is,` atleast about l0() to"3v()0A p'.s.i.g., kdepending upon the type of feed inateri'a'l andthe polymerization temperature. 'Higherpressuresup/to 500 to' 700 p.sli.g.`or h'i'ghercan be used,ifdesire/d.L The'catalys't concentration in the "reactor usually varies from' between about O10 and about l0 Vp'elc'ent'by weight and generally, it is dNl able to provide a reactant residence time of betweenabut The 'use 0f a dilu'ent thi polymeriz'atiti'rctiii in genral serves two pur'posesr. Siiicefthe reactis are 'usually exo'therm'ic in nature, the `presence'of fa' qiintity of dilunt provides' a'riithd for b'fa'iilig clse Cont l f the reaction temperature.- In additio'ii, as prev stated,polymers"formed in there'a'ction or aportio'thfereof may be tacky in nature and, if this is the cas, the presence of a dil'ent tends to` prevent adherence of the polymer to the walls 'of the reaction vessel and therercovery"equrpir'lent which isvused in treating the ein nt from/the'polymeriiation reaction. 'Ingenerh the; tity ofdilue'nt is large 4relative to the' oletirlfeed" aterial. ."Usually, vt'l'eoleliir ciistitutesfbet'wee'riaboit O1 'and about 25'perce`r`1`t by volume of tliem'irtture and p f- The 'solvent div-aiment empie'yed in ,the polymeren n reaction includes in general,l parain( hydro'c ,s. Among, the more useful solvents are a'czyclicxvl/"l'ydrocarn @de erarbeiteten? .3. @bw-12e isooctane," etc., y'arid prete -bly depend 'onV be `employe ticularly in processes for the polymerization of ethylene Following this, excess clY in" carrying-'dpt under conditions which provide polymers of ethylene which have a density of at least 0.94 and preferably 0.96 or higher and a crystallinity of at least 70 percent and preferably at least 80 percent at normal atmospheric temperatures. While the polymerization of ethylene provides a preferred embodiment of the invention, it is not intended that the scope of the invention be limited thereby but that any of the other processes described are also within the invention.

One method of preparing polymers of olens is de scribed in detail in a copending application of Hogan and Banks, Serial No. 573,877, filed March 26, 1956. This particular method utilizes a chromium oxide catalyst, preferably containing hexavalent chromium, with silica, alumina, silica-alumina, zirconia, thoria, etc. In the method of the Hogan et al. application, olefins are polymerized in the presence of a hydrocarbon diluent, for example, an acyclic, or aromatic compound which is inert and in which the formed polymer is soluble. The reaction is ordinarily carried out at a temperature between about 150 F. and about 450 F. and under a pressure suicient to maintain the reactant and diluent substantially in the liquid state. The polymers produced by this method, particularly the polymers of ethylene, are characterized by having an unsaturation which is principally either trans-internal or terminal vinyl, depending on the particular process conditions employed. When low reaction temperatures, about 150 F. to about 320 F., and a mobile catalyst are used for polymerization, the product polymer is predominantly terminal vinyl in structure. When polymerization is carried out at higher temperatuers and a fixed catalyst bed, the polymer has predominantly trans-internal unsaturation. Polymers prepared by both methods are also characterized by their high densities and high percentage of crystallinity at normal atmospheric.

When preparing olefin polymers using the methods and catalysts previously described, a portion of the olefin feed is often converted to heavy polymers of substantially higher molecular weight than the desired polymer product. These heavy polymers which are almost insoluble in the diluents (and at the temperatures) employed in the polymerization reaction frequently become associated with the catalysts solids. It is not unusual for the catalyst to pass through the entire catalyst recovery system and emerge contaminated with substantial quantities of the heavy polymers. For example in the polymerization of ethylene using the method and catalysts of Hogan and Banks (Serial No. 573,877) the recovered catalyst can contain from about 25 percent to about 80 percent of polymer by weight. Similar high concentrations of heavy, substantially insoluble polymer, associated with the polymerization catalyst, are encountered in systems employing other feed materials, catalysts and different reaction conditions.

In carrying out the process of this invention in one of its embodiments a polymer solution, for example, a solution of solid ethylene polymer, containing finely sub-divided solids, such as chromium oxide catalyst, containing hexavalent chromium, associated with silica-alumina, said catalyst having associated therewith between about 25 percent and about 80 percent by weight of heavy, substantially insoluble polymers, is reduced in temperature to the level at which polymer begins to precipitate from solution. Preferably this operation is carried out under conditions of mild agitation. The initial precipitation temperature will vary depending on the particular polymer being treated, and the solvent in which the polymer is dissolved. For example when treating an ethylene polymer dissolved in cyclohexane precipitation usually begins in a temperature range of between about 230 and about 200 F. When treating other polymers in the various solvents which are employed in carrying out 4 perature can vary over a relatively wider range, such as from about 300 to about 200 F.

When the initial polymer precipitation temperature is reached a portion of dissolved polymer is released from solution and the particles of catalyst adhere together and agglomerate. To provide the best separation it is desirable that the temperature reduction continue beyond the point of initial precipitation whereby a larger amount of polymer is precipitated and additional agglomeration of the catalyst is provided. Usually the cooling process is continued until the catalyst agglomerate contains between about percent and about 95 percent of polymer by weight. When treating ethylene polymer in cyclohexane this occurs when the temperature reaches between about 210 and about 190 F. When processing other polymers, dissolved in the various solvents previously discussed, the temperature range of maximum agglomeration is between 250 F. and 200 F., depending on the particular polymer and solvent being treated.

At this point the cooling process is terminated and the agglomerated solids and remaining polymer solution are heated, whereby the temperature is increased and a portion of the precipitated polymer is re-dissolved. It has been found that the heating operation can be continued until the temperature of the solution reaches a level greater than the temperature at which initial polymer precipitation occurred during the cooling operation, without dispersing the agglomerated solids. Thus, when recovering catalyst from a solution of ethylene polymer `in cyclohexane re-heating can be continued until the solution reaches a temperature of between about 2 F. and about 20 F. above the initial precipitation temperature thus, providing a iinal heated solution having a temperature of between about 250 F. and about 202 F. In general, the temperature differential noted will apply in the treatment of other polymers dissolved in other solvents.

Following the re-heating process, during which the concentration of polymer in the catalyst agglomerates is reduced to between about 50 and about 90 percent by weight, the agglomerates are removed from the polymer solution by a suitable separation procedure such as for example, by filtering, centrifugation, etc.

Although the mechanism of solids agglomeration, within the scope of this invention, is not clearly understood it is believed that an important factor is the heavy polymer associated with the catalyst solids. It is believed that the changes in temperature which bring about agglomeration effect changes in the polymer properties whereby the particles of solids become adherent to each other and thus form agglomerates.

It is known that precipitation of soluble polymer from solution aids in the agglomeration, however, agglomeration does occur without appreciable polymer precipitation; therefore, this does not appear to be an essential feature of the agglomeration process.

In accordance with another embodiment of the invention, a further treatment of the agglomerated solids is provided whereby a substantial portion of the polymer associated with the agglomerates is removed. In carrying out this embodiment the agglomerated solids are mixed with solvent in an amount usually between about 5 and about 20 lbs./lb. of agglomerated solids and the mixture is heated whereby the temperature is raised to a suicient level to assure dissolution of at least a portion of the polymer associated with the solid agglomerates. When dissolving ethylene polymer in cyclohexane the temperature is usually increased to between about 250 and about 350 F. Following this step the polymer solution and solids are passed through a separation step wherein separation between the solids and solution is effected. Usually it is preferred to combine the separated solution with the polymer solution originally separated from the agglomerated catalyst, whereby a single the polymerization reaction the initial precipitation tem- 75 polymer solution yield stream is obtained.

In order to more clearly-'describe theknyetionfand `,providea better understanding thereof reference is had litho vthe"Accompanying drawingl'which is a diagrammatic :illustration .of a polymerization reactor',` an ethylene.

yremoval vessel, a cooling vessel, a'heatexchangeram assolids 'separation apparatus'suitable for the' performance of this invention. Referringtolthe drawingethyl ene, cyclohexane diluent fand chromium orgide catalyst ikare introduced to reactor ,8 `througlrconduits 2, 4 and 16, respectively. For easeiofhadling, the catalyst 'is slurried "in ,c'yclohe'xane before it "is introduced to the reactor. VDuring polymerization the-materialiin'the `re-V actor is maintained in ashighly lagitated's'tate by means);A

temperature o f about 285 v,F. and a pressure of ,about 500 p.s.i.a. and for a suicient periodof time-to vconverta `portionfof the ethylene feed ,to ksolid ethylene .of a Ymechanical mixer vor other conventional mixing means (not shown); ylhe'reaction is carried out at a' polymer (at ambient temperatures). `gle'acti'on efliuent leaves the reactor throughcond'uit'll 'andenter's .a separationzone 12 wherein a strea'mcompri'sing 4principally v unconverted ethylene and some solvent isseparated vand returned to the reaetorthrough conduit 1,4 Tand cooler io. Followingthis step, the effluent .is combined ,with additional solvent introducedthrougli conduit '18. The mixture, comprising a solution of solid ethylene polymer in cyclohexane containinga finely sub-,divided ,catalyst is then introduced to precipitatorvessel 24. This `vessel comprises a confined cylinder having disposed thereiny Ia `cylindricalfsection 28 oflesser diameter openly comvvr'nunicatin'g with the confined cylinder` in the upper portion thereof. Feed solution from conduit is intro- "duced to the inner section V28`wherein cooling precipitation of polymer and agglomeration of the catalyst takes place. The coolingis provided byreducing the pressure on the precipitator vwherebycyclohe'xane isi.l

reduction in pressure pass overhead from the precipitator through conduit 32 andare condensed in ,condenser 34. In order to minimize foaming in the precipitator and lalso to maintain a substantially constant concentration of cyclohexane solvent the `condensed cyclohexane is '.'r'eturlned to the precipitator through conduit 35v and sprayst). As desired however, 'a portion ofthe solvent 'can be passed from the system 'through conduit 35.

As the feedv solution passes upwardly through section 28 the temperature decreases, polymer precipitates from solution and the catalyst particles lare agglomerated. The material leaving this section comprises polymer solutionand'catalyst agglomerated with'about 95 percent,l polymer by weight at a temperature of about 200 F;

Although the continuous introduction of feed solution is in itself suicent to provide passage of the agglomerated solids from section 28 removal of the solids is also aided by vapor-ization Yof cyclohexane in the feed solution which has a buoyant effect whereby solids are floated to the top of this section. A mixture of polymer solution and agglomerated solids overows into section 6 and is withdrawn from the bottom of vessel 24through conduits 38, in the form of a slurry. This material is passed Avia pump 40 throughheat exchanger 42 where the slurry temperature is increased'to Va level above above the temperature at which precipitation was initially effected from the feed. As a result of the heating step the concentration of polymer in the catalyst agglomerates is reduced from about 95 percent by weight to about 85 percent. The material leaving heater 42 enters solids separation zone 44, for example arlilter, centrifuge or the like, wherein the polymer solution and agglom-v erated solids are separated. The polymer solution is yielded through conduit 58Vand the agglomerated solids are recovered through conduit 46.

In this particularembodiment of the invention a further processing operation is provided whereby the cata- 'vaporized 'from theV polymer solution 'and the 4solutionf.l `'temperature is decreased...` 'I he vapors released by theV the mixture being/passed"throughheater v50 wh" eb a.r v'portion'ofthenpolymer remaining associated wit .fthe agglomerated ,solids is dissolved inthe polymers'oltion. lhefsolids areithenfpassed to a secondary solids separationvzone 52 from' which polymer solution is recoveredv through conduit p56, being combined with the polymer solution in conduit 58, and catalyst solids are yielded through conduit 54. f Y Y The preceding embodiment of the inventionhas been fdescribed in conjunction with a specific frapparatusar- -.rangement, however, this :is not intended in any wayl to limit 'the scope of fthe jinvention. VFor example,itl;is

within the scopeof the invention to transfer the l'"heat exchangerAiZl to section 26 of vessel 24, suchgfasiby' installing a heating coil in the-lower portion of section 26 `or by useiof a', double walled precipitator vesserwrm 'i a heatingffluid betweenthe'inner and outer Walls'. Y"It is also within the scope of the invention to provide cooling of the polymer Vsolution-and agglomration of the chromium catalyst other `than by auto-refrigeration,f;as

shown in rthe drawing. Y v Y Y s I Y The .following data/is presented to illustrate thel inven- "tion'inone embodiment-thereof: Y 1 2 EXAMPLE -r A solid polymerof ethylene was prepared in 'thepresence of a catalyst comprisingl 2.5 percent' by weight of 4cl'irornium as chromium oxide, containing..2.2 percent hexavlalentchromium, withsilica-alumina"(weighty ratio Sz-1),; prepared by impregnating silica-alumina withfan ,s'aqueouls `solution of .chromiuni trioxide, followed "by drying and activation `,in dry air at gradually` Vincreasing temperatures upto 950YF. v y e vA sample of the catalyst-containing ethylene polymer solution was diluted withcyclohexaneand heated Aat 300 F. toprovide a 4 weightpercent polymersolution. The solution was cooled to 225 F. ina Jergusongauge'glass and agitation was commenced. The vtemperature ofthe solution was further decreased and vv at. approximately 210 F. the catalyst particles started'toy grow. ``Betwejen ,205 and 200 Fthe catalyst agglomeratesbecamequite large land the solution, whichbefore had beencloudy,

began to clear. The reduction in temperature wasfcontinued down tol 190o F. beforethe solution became f draw catalyst agglomerates amount of occluded polymer, less than the amount assosubstantially clear (indicating complete catalyst agglomeration). Cooling was continued down'to,180 F. at which point the procedure was reversed and heating of the solution was commenced. The solution appeared` g;

even clearer and more iiuid'at 205 KF. than it did during the cooling cycle.

ciated with the catalyst during the cooling cycle.

The catalyst agglomerates did not start to break up until the temperature reached about 216 F. even with mild agitation.` Bythe time the temperature reached 221 VF. most of the .catalyst `particles had returned to their original size (similar in appearance to -their con# H ditions preceding-the cooling cycle). Both the cooling` and heating cycles were carried outat time temperature rates of about one degree Fahrenheit per minute.

EXAMPLE II At this point it waslpossible to withj containing a minimum' Cooling cycle (at a rate of about 1 F./mnute)Y [Heated solution to 250 F. to put all of th polymer in solution] 210 F.-Some good size particles formed.

Heating cycle (ata rate of about 1 F./minute) 205 F.$till about the same. 210 F.Still about the same. 215 F.-Agglomerates breaking up some.

At `this point it was possible to withdraw catalyst agglomerates containing a minimum amount of occluded polymer, less than the amount associated with the catalyst during the cooling cycle.

219 F.-Agglomerates breaking up quite rapidly. 223 F.-Agglomerates -fairly well dispersed, solution cloudy.

1. A process for recovering solids consisting essentially I of supported chromium oxide catalyst from a solution lyst solids from the polymer solution before redispersal of said solids.

2. The process of claim 1 in which the solids consist essentially of chromium oxide catalyst containing hexavalent chromium associated with silica-alumina and the polymeris a solid .polymer of ethylene.

3. A process for recovering solidsconsisting essentially of supported chromium oxide catalyst from a solution of normally solid polymer of a l-olen having a maxi- '.mum of 8 carbon atoms per molecule and no branching nearer the double bond than the 4-position, said polymer having an initial precipitation temperature between 330 f F. and 200 F., which comprises reducing the temperature of a normally solid polymer of a l-olen having a maximum of 8 carbon atoms per molecule and no branching nearer the double bond than the 4-position which comprises reducing the temperature of the polymer solution to the level where polymer begins to precipitate, continuing the reduction in temperature until additional polymer precipitates and the solids agglomerato, increasing the temperature of the polymer solution to a level above the temperature at which the polymer 'initially precipitated whereby a portion of the precipitated polyf mer is redissolved and separating the agglomerated cataof the polymers solution to between about 250 and about 190 F. whereby polymer precipitates from solution and the solids agglomerate, increasing the temperature of the polymer solution to between about 320 F. and 202 F. whereby a portion of the precipitated polymer is redissolved and separating the agglomerated solids from the polymer solution.

4. The process of claim 3 in which the solids consist essentially of chromium oxide containing hexavalent chromium associated with silica-alumina and the olefin polymer is a solid polymer of ethylene.

5. A process for recovering solids consisting essentially of supported chromium oxide catalyst from a solution of normally solid ethylene polymer which comprises reducing the temperature of the polymer solution to between about 230 F. and about 200 F. whereby polymer begins to precipitate from solution, continuing the temperature reduction of the solution until additional polymer precipitates and the solids agglomerate, increasing the temperature of the polymer solution to between about l250 F. and 202 F. whereby a portion of precipitated polymer is redissolved and separating the agglomerated solids from the polymer solution.

6. The process of claim 5 in which the solids consist essentially of chromium oxide containing hexavalent 'chromium associated with silica-alumina.

References Cited in the tile of this patent UNITED STATES PATENTS KARL H. AXLINE Attesting OHcer UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIGN WllamL. Stalder It is hereby certified that error a of the' above numbered patent requiring c Patent should read as corrected below.

ppears in the printed specification orrection and that the said Letters Signed and sealed this 31st day of January 1961.,v

(SEAL) Attest:

ROBERT c. WATsoN Commissioner of Patents 

1. A PROCESS FOR RECOVERING SOLIDS CONSISTING ESSENTIALLY OF SUPPORTED CHROMIUM OXIDE CATALYST FROM A SOLUTION OF A NORMALLY SOLID POLYMER OF A 1-OLEFIN HAVING A MAXIMUM OF 8 CARBON ATOMS PER MOLECULE AND NO BRANCHING NEARER THE DOUBLE BOND THAN THE 4-POSITION WHICH COMPRISES REDUCING THE TEMPERATURE OF THE POLYMER SOLUTION TO THE LEVEL WHERE POLYMER BEGINS TO PRECIPITATE, CONTINUING THE REDUCTION IN TEMPERATURE UNTIL ADDITIONAL POLYMER PRECIPITATES AND THE SOLIDS AGGLOMERATE, INCREASING THE TEMPERATURE OF THE POLYMER SOLUTION TO A LEVEL ABOVE THE TEMPERATURE AT WHICH THE POLYMER INITIALLY PRECIPITATED WHEREBY A PORTION OF THE PRECIPITATED POLYMER IS REDISSOLVED AND SEPARATING THE AGGLOMERATED CATALYST SOLIDS FROM THE POLYMER SOLUTION BEFORE REDISPERSAL OF SAID SOLIDS. 